Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
  • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
  • C08F299/08—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polysiloxanes
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/075—Silicon-containing compounds
  • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
  • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer

Definitions

• the present invention relates to a high sensitivity light-sensitive lithographic printing plate material improved in developability, printing property and plate preservation stability after processing the plate.
• a light-sensitive lithographic printing plate material in which a developing treatment is carried out with a neutral developing solution with a pH of less than 9 or an aqueous alkali solution having a pH in the range of 9 to 12.
• CTP computer to plate
• JP 2001-290271A Patent Literature 1
• JP 2002-278066A JP 2003-43687A
• JP 2003-43687A examples of a lithographic printing material suitable for the CTP with high sensitivity and excellent in printing endurance
• Patent Literature 2 JP 2002-278066A, JP 2003-43687A, etc.
• JP 2006-39177A Patent Literature 3
• JP 2006-64952A Patent Literature 4
• These techniques are mainly intended to avoid background stain caused by development failure which became a problem when an alkaline developing solution having a pH of 12 or lower is used. It is essential for avoiding such a background stain to heighten developability of the light-sensitive lithographic printing plate material.
• the problem of easily causing background stain due to plate preservation also markedly relates to the characteristics of the surface of the support to be used.
• a support to be frequently used in the said field there have been known an aluminum plate having a surface which had been subjected to surface roughening treatment and anodized, or a support having a hydrophilic layer containing colloidal silica at the surface thereof as herein below mentioned JP 2008-265297A (Patent Literature 5), etc.
• Patent Literature 5 JP 2008-265297A (Patent Literature 5), there is disclosed an example of a light-sensitive lithographic printing plate material which is capable of developing with water.
• a light-sensitive lithographic printing plate material which comprises a photo-curable light-sensitive layer containing a polymer having both of a sulfonic acid group and a phenyl group to which a vinyl group is bonded through a hetero ring at the side chain is provided on a support to which a specific hydrophilic layer is provided.
• developability is far low as compared with the case where the above-mentioned alkaline developing solution is used, so that there are problems that effects on developability due to fluctuation of the development temperature or film thickness at the non-image portion, etc., or effects on occurrence of background stain due to invasion into fine pores of the photo-curable light-sensitive layer and worsening of background stain after plate preservation, etc., are extremely markedly revealed.
• a gum-coating treatment is carried out on the surface of a printing plate in many cases after exposure and developing treatment at the time of preparing the plate.
• occurrence of background stain relating to plate preservation can be improved with a certain extent, but it is not in a sufficient level, and it has further been desired to realize a printing plate which does not cause background stain by plate preservation without applying the gum treatment.
• a lithographic printing plate raw plate which is excellent in printing endurance and particularly excellent in endurance to a plate cleaner in a lithographic printing material which comprises an alkali soluble polyurethane binder such as polydimethylsiloxane, etc., containing an organopolysiloxane group. It is certainly improved in printing endurance by incorporation of a polysiloxane group, but a tendency of lowering alkali developability is remarkable due to the incorporation.
• An object of the present invention is to provide a light-sensitive lithographic printing plate material which has high sensitivity, causing no background stain even when a developing treatment is carried out with a neutral developing solution having a pH of less than 9 or an alkali developing solution having a pH range of 9 to 12, causing no background stain even when the plate was allowed to stand for a long period of time after developing treatment or during printing even when no gum-coating treatment is carried out, and providing excellent printing endurance and ink transfer property.
• the problems of the present invention can be basically solved by the following method. That is, in the photo-curable light-sensitive layer on the support, the light-sensitive lithographic printing plate material contains a polymer synthesize by using at least a compound represented by the following-mentioned general formula I and having a polymerizable double bond group and at least one of a carboxyl group and a sulfonate group at the side chain.
• R 1 , R 2 and R 3 each independently represent an alkyl group or an alkoxy group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms, provided that at least two of R 1 , R 2 and R 3 represent alkoxy groups.
• Y 1 represents an alkylene group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms.
• a light-sensitive lithographic printing plate material having high sensitivity, causing no background stain even when a developing treatment is carried out with a neutral developing solution having a pH of less than 9 or an alkali developing solution having a pH range of 9 to 12, causing no background stain even when the plate was allowed to stand for a long period of time after developing treatment or during printing even when no gum treatment is carried out, and providing excellent printing endurance and ink transfer property.
• a general explanation concerning a polymer synthesized by using a compound shown by the general formula I is firstly carried out. That is, the compound shown by the general formula I has a mercapto group in the molecule, so that it acts as the so-called chain-transfer agent which is well known in a radical polymerization reaction. A hydrogen atom is withdrawn from the mercapto group by a radical which is an active intermediate formed in the radical polymerization reaction to generate a sulfur radical. It has been well known that by adding the sulfur radical to the monomer, a radical polymerization is re-started and a polymer in which the sulfur atom is bonded to the terminal is formed.
• the characteristic feature of the compound represented by the general formula I to be used in the present invention resides in having a silicon atom to which at least two alkoxy groups are bonded simultaneously in the structure.
• the alkoxy groups bonded to the silicon atom are easily hydrolyzed in the presence of water to form a hydroxyl group(s) in some cases.
• the hydroxyl groups formed by the hydrolysis are condensed to each other to form a —Si—O—Si— bond in some cases.
• the following two polymers can be obtained as a polymer having a polymerizable double bond group, and a carboxyl group or a sulfonate group at the side chain.
• the first case is a case of a polymer having a group represented by the following general formula II at the end of the main chain of the polymer.
• the inventors have found that the light-sensitive lithographic printing plate material specifically comprising the following constitution can solve the problems to be solved by the present invention. That is, it is a light-sensitive lithographic printing plate material which contains a polymer having a group represented by the following general formula II at the end of the main chain and having a polymerizable double bond group, and a carboxyl group or a sulfonate group at the side chain in the photo-curable light-sensitive layer on the support.
• R 4 , R 5 and R 6 each independently represent a hydroxyl group, an alkyl group or an alkoxy group each having 1 to 10 carbon atoms, preferably having 1 to 6 carbon atoms, further preferably having 1 to 4 carbon atoms, provided that at least two of R 4 , R 5 and R 6 represent hydroxyl groups or alkoxy groups.
• Y 2 represents an alkylene group having 1 to 10 carbon atoms, preferably having 1 to 6 carbon atoms, further preferably having 1 to 4 carbon atoms.
• Another case is a case where the groups represented by the above-mentioned general formula II are condensed by dehydration to form a —Si—O—Si— bond, whereby the terminal groups of the polymers are bonded to form a polysiloxane.
• the inventors have found that the light-sensitive lithographic printing plate material comprising the following constitution can solve the problems to be solved by the present invention in this case.
• a light-sensitive lithographic printing plate material comprising a photo-curable light-sensitive layer on a support, which contains a polymer in which a unit having a polyorganosiloxane structure, and a unit having a polymerizable double bond group, and a carboxyl group or a sulfonate group at the side chain being bonded through a sulfur atom.
• m represents an added molar number of the monomer M, and it shows that the RS group binds to the ⁇ terminal of the polymer with a polymerization degree of m and the hydrogen atom binds to the ⁇ terminal of the same by the polymerization.
• R in the formula represents —Y 1 —Si(R 1 )(R 2 )(R 3 ) of the above-mentioned formula I, and m represents an integer in the range of 2 to 1000, more preferably an integer in the range of 10 to 100.
• the preferred amount of the mercapto compound to be added to the monomer M is preferably in the range of 0.5 to 60 mol % as described below, more preferably in the range of 1 to 40 mol %.
• various conditions such as a kind and an amount to be added of the polymerization initiator, a polymerization temperature, a monomer concentration, etc., are not particularly limited and can be selected from the range well known in the art.
• a polymer in which the group RS— is introduced into the ⁇ terminal of the polymer main chain having various functional groups, and the hydrogen atom (—H) is introduced into the ⁇ terminal of the same is synthesized.
• the mercapto compound (R—SH) to be used the mercapto compound represented by the above-mentioned formula I is used, and various monomers mentioned below are polymerized in the presence of the above compound to obtain an objective polymer of the present invention.
• Particularly preferred examples of the compound represented by the general formula I may be mentioned 3-mercaptopropyl(dimethoxy)methylsilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyl(diethoxy)methylsilane, 3-mercaptopropyltriethoxysilane, etc.
• a monomer which is to provide a polymerizable double bond group at the side chain and a monomer having a carboxyl group or a sulfonate group are copolymerized to obtain an objective polymer.
• the monomer having a carboxyl group herein used is firstly explained.
• the monomer having a carboxyl group which can be used in the present invention may be specifically mentioned and preferably used an acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, partially esterified maleic acid, and various kinds of carboxyl group-containing monomers shown by the following chemical formulae.
• the monomer having a sulfonate group which is another element for constituting the polymer of the present invention is explained.
• Examples of such a monomer having a sulfonate group may be mentioned an alkali metal salt, amine salt and quaternary ammonium salt of vinylsulfonic acid, an alkali metal salt, amine salt and quaternary ammonium salt of styrenesulfonic acid, an alkali metal salt, amine salt and quaternary ammonium salt of acrylamide-2-methylpropanesulfonic acid, an alkali metal salt, amine salt and quaternary ammonium salt of allylsulfonic acid, an alkali metal salt, amine salt and quaternary ammonium salt of methallylsulfonic acid, an alkali metal salt, amine salt and quaternary ammonium salt of methacrylic acid 3-sulfopropyl ester, etc., as preferred examples.
• the alkali metal salt herein mentioned means a sodium salt, potassium salt and lithium salt
• the amine salt means a salt formed by amines such as ammonia, triethylamine, tributylamine, monoethanolamine, diethanolamine, triethanolamine, dimethylaminoethanol, diethylaminoethanol, methylaminoethanol, ethylaminoethanol, n-butyldiethanolamine, t-butyldiethanolamine, etc., as an amine
• the quaternary ammonium salt means a salt formed by using tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide, tetrabutyl ammonium hydroxide, choline, phenyltrimethyl ammonium hydroxide, or benzyltrimethyl ammonium hydroxide.
• the monomer herein mentioned may be mentioned two types of monomers, one of which is a monomer which gives the polymer having a polymerizable double bond group at the side chain by polymerizing itself according to the above-mentioned scheme I, and the other is a monomer in which at the step of polymerizing the monomers by the above-mentioned scheme I, no polymerizable double bond group is yet introduced into the side chain, and it is used to introduce the polymerizable double bond group into the polymer obtained by the polymerization according to the above-mentioned scheme I.
• the former i.e., the monomer which gives the polymer having a polymerizable double bond group at the side chain by polymerizing itself
• a (meth)acrylic acid allyl ester In the case of this monomer, there exist two polymerizable double bond groups in the molecule, and there is remarkable difference in polymerizability between that of the (meth)acryloyl group and that of the other allyl group.
• the polymerizability of the former is markedly high so that polymerization predominantly proceed with the (meth)acryloyl portion, so that a polymer in which an allyl group is pendanted at the side chain can be formed.
• the obtained polymer becomes a polymer in which an allyl group which is a polymerizable double bond group is bound to the side chain.
• the monomer having two kinds of polymerizable double bond groups having markedly different polymerizability in the molecule may be mentioned the monomers shown below. In these examples, all of which having a (meth)acryloyl group or a styryl group as a higher polymerizability group, and having a vinyl acetate ester group, a vinyl ether group or an allyl group as a lower polymerizability group are exemplified.
• the vinyl acetate ester group is a group having extremely high polymerizability when it is present alone, but in the copresence of a (meth)acryloyl group or a styryl group, polymerization of the vinyl acetate ester group is hardly caused until the latter is consumed by polymerization so that this property is utilized. Accordingly, when the polymer of the present invention is to be synthesized by using the monomer having two kinds of polymerizable double bond groups in the molecule, it is preferred to obtain a polymer at the stage at which the polymerizable double bond group with a lower polymerizability is not yet polymerized by stopping the polymerization during the same without completing the polymerization.
• a monomer hereinafter referred to “a precursor monomer” to be used for introducing a polymerizable double bond group into the side chain subsequent to the polymerization of the scheme I is explained.
• the monomer which can be used as a precursor monomer is a monomer having both of the polymerizable double bond group and further other reactive group, and as the said reactive group, there may be mentioned a hydroxyl group, carboxyl group, amino group, mercapto group, epoxy(glycidyl) group, isocyanate group, haloalkyl group, acid anhydride group, amino group and other well known reactive groups.
• Examples of the compound which can be used as the precursor monomer may be mentioned hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, glycidyl(meth)acrylate, mercaptomethylstyrene, aminostyrene, chloromethylstyrene, chloroethylvinyl ether, maleic anhydride, dimethylaminoethyl(meth)acrylate, diethylaminoethyl(meth)acrylate, etc.
• the compound which can be particularly preferably used as the above-mentioned precursor monomer there may be mentioned a compound in which a mercapto group is bonded through the heterocyclic ring group represented by the following general formula III.
• L 1 represents a linking group
• R 7 represents a hydrogen atom or a methyl group
• p represents 1 or 2.
• Z 1 represents a heterocyclic ring group.
• linking group of L 1 there may be mentioned an oxygen atom, sulfur atom, alkylene group, alkenylene group, arylene group, —N(R a )—, —C(O)—O—, —C(R b ) ⁇ N—, —C(O)—, sulfonyl group and a linking group in which the above are complexed.
• R a and R b are each represents a hydrogen atom, alkyl group, aryl group, etc.
• the above-mentioned linking group may have a substituent(s) such as an alkyl group, aryl group, halogen atom, etc.
• a carbon number of the alkylene group and the alkenylene group possessed by the linking group L 1 of the general formula III are preferably in the range of 1 to 20, and a carbon number of the arylene group is preferably in the range of 6 to 20.
• a nitrogen-containing heterocyclic ring such as a pyrrol ring, pyrazole ring, imidazole ring, triazole ring, tetrazole ring, isoxazole ring, oxazole ring, oxadiazole ring, isothiazole ring, thiazole ring, thiadiazole ring, thiatriazole ring, indole ring, indazole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzthiazole ring, benzselenazole ring, benzothiadiazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, quinoline ring, quinoxaline ring, etc., a furan
• the mercapto group bound to the heterocyclic ring group As a characteristic feature of the mercapto group bound to the heterocyclic ring group as mentioned above, there may be mentioned a characteristic that it has higher acidity as compared to the mercapto group bound to an alkyl group.
• Such a mercapto group bound to the heterocyclic ring group can be neutralized by addition of, for example, an organic amine, etc., as a relatively weak base, etc., to form a salt in some cases.
• the function of the mercapto group as a chain transfer group is lowered by forming a salt with an organic amine, etc., so that the above-mentioned compound can form a precursor polymer before introducing the polymerizable double bond group at the side chain by carrying out polymerization (scheme I) using a usual radical polymerization initiator.
• the mercapto compound of the above-mentioned general formula I does not form a salt in the presence of a weak base such as an organic amine, etc., and has high chain transferability
• the above-mentioned precursor polymer can be formed.
• a compound which can be preferably used as the above-mentioned organic amine there may be preferably used compounds such as ammonia, triethylamine, monoethanolamine, diethanolamine, triethanolamine, dimethylaminoethanol, diethylaminoethanol, methylaminoethanol, ethylaminoethanol, n-butyldiethanol amine, t-butyl-diethanol amine, etc.
• a polymerizable double bond group By adding a compound having a polymerizable double bond group which can bind to the above-mentioned precursor monomer to a precursor polymer, a polymerizable double bond group can be introduced into the side chain of the precursor polymer.
• a compound having the polymerizable double bond group may be used various kinds of compounds already known as a monomer having a reactive group.
• the reactive group there may be mentioned a hydroxyl group, a carboxyl group, an amino group, a mercapto group, an epoxy(glycidyl) group, a haloalkyl group, an acid anhydride group and other known reactive groups.
• Preferred examples of the compound which can be used as the monomer having a reactive group there may be mentioned hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, glycidyl(meth)acrylate, chloromethyl-styrene, chloroethylvinyl ether, maleic anhydride, dimethylaminoethyl(meth)acrylate, diethylaminoethyl(meth)acrylate, etc.
• chloromethylstyrene can be mentioned as the most preferred monomer having said reactive group.
• the reaction generated by the combination of the mercapto group and chloromethylstyrene can proceed under mild conditions with high yield so that it can be extremely preferably used.
• a precursor polymer is synthesized by using chloromethylstyrene as a precursor monomer, then, by adding mercaptomethylstyrene or a compound represented by the above-mentioned formula III as a monomer having a reactive group to introduce the polymerizable double bond group into the side chain of the precursor polymer to react them to obtain the polymer of the present invention with high yield, whereby the method can be preferably used.
• a vinyl group bonded to the phenyl group is used as a polymerizable double bond group to be introduced into the side chain of the polymer of the present invention, it is particularly preferred since the reactivity of said vinyl group is high. Moreover, it is particularly preferred that the vinyl group is bonded to the phenyl group which is linked through a heterocyclic ring. In this case, it is characteristics that it has good photocurability, and showing no curing inhibition by oxygen, further is stable with a lapse of time, and shows good photocurability without applying any heat treatment after photo-irradiation. Preferred examples of such a polymerizable double bond group to be introduced into the side chain are shown below with the general formula IV.
• L 2 and Z 2 in the general formula IV are the same with L 1 and Z 1 in the general formula III mentioned above, respectively.
• q represents 1 or 2.
• the polymer of the present invention which is soluble in an alkali developing solution having a pH in the range of 9 to 12 can be obtained. Or else, when the above-mentioned monomer having a sulfonate group is to be used, the polymer of the present invention which is soluble in a neutral developing solution having a pH of less than 9 can be obtained.
• styrene derivatives such as styrene, 4-methylstyrene, 4-acetoxystyrene, 4-methoxystyrene, etc.
• various alkyl(meth)acrylates such as methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate, etc.
• monomers having a nitrogen-containing heterocyclic ring such as 4-vinylpyridine, 2-vinylpyridine, N-vinylimidazole, N-vinylcarbazole, etc.
• a monomer having a quaternary ammonium salt group there may be used a quaternarized material by methyl chloride of 4-vinylbenzyltrimethyl ammonium chloride, (meth)-acryloyloxyethyltrimethyl am
• these monomers are preferably contained in an amount of 20% by weight or more and 70% by weight or less, more preferably 30% by weight to 70% by weight, further preferably 35% by weight to 70% by weight based on the total composition as 100% by weight. If they are less than the above ratio, there is a case where the copolymer does not dissolve in an alkali developing solution having a pH in the range of 9 to 12 or in a neutral developing solution having a pH of less than 9. Moreover, when the ratio of these monomers contained in the copolymer exceeds 60% by weight, there is a case where sufficient printing endurance cannot be obtained.
• Examples of the polymer having a group represented by the above-mentioned formula II at the end of the main chain of the polymer, and having a polymerizable double bond group and a carboxyl group at the side chain preferably used in the present invention are as mentioned below.
• the numerals in the FIGURE represent a ratio of the copolymer composition (weight ratio).
• a terminal group structure is shown at the left end of the chemical formula of the FIGURE, and in the terminal group structure, the alkoxy group bonded to the silicon atom includes the case where it is turned into a hydroxyl group by hydrolysis reaction.
• the polymer having a group represented by the above-mentioned formula II at the end of the main chain, and a polymerizable double bond group and a carboxyl group at the side chain there may be mentioned a polymer in which the polymerizable double bond group is a phenyl group to which a vinyl group is bonded through a hetero ring as disclosed in, for example, JP 2001-290271A. Examples of such a polymer are shown below.
• the numerals in the FIGURE represent a ratio of the copolymer composition (weight ratio).
• Examples of the polymer having the group represented by the above-mentioned formula II at the end of the main chain of the polymer and having a polymerizable double bond group and a sulfonate group at the side chain which can be preferably used in the present invention are shown below.
• the numerals in the FIGURE represent a ratio of the copolymer composition (weight ratio).
• the polymer having the group represented by the above-mentioned formula II at the end of the main chain of the polymer and a polymerizable double bond group and a sulfonate group at the side chain there may be mentioned a polymer having a sulfonate group and a phenyl group to which a vinyl group is bonded through a hetero ring as described in, for example, JP 2008-265297A.
• the most preferred examples of said binder polymer are mentioned below.
• the numerals in the FIGURE represent a ratio of the copolymer composition (weight ratio).
• the mercapto compound of the general formula I has at least two or more alkoxy groups in the molecule, and the alkoxy group is easily hydrolyzed in water in the presence of an acid or an alkali to become a hydroxyl group as well known in the art. It is also well known that the hydroxyl group is dehydrated or condensed to form a polysiloxane bond to form a polymer or an oligomer depending on the conditions.
• a molar number of the mercapto compound of the general formula I is 10 mol % or less based on the molar number of the whole monomer to be used, preferably 0.5 mol % to 10 mol %, and further preferably 1 mol % to 10 mol %.
• a molecular weight of the formed polymer of the present invention is preferably, in terms of a weight average molecular weight, in the range of 5,000 to 200,000, more preferably in the range of 10,000 to 200,000, further preferably in the range of 20,000 to 150,000. If the molecular weight is larger than the above range, a ratio of the group of the general formula II as the terminal group occupied in the polymer is small so that the effects of the present invention cannot be obtained in some cases. Also, when the weight average molecular weight is less than 5,000, when it is utilized in the light-sensitive lithographic printing plate material mentioned below, printing endurance is inferior in some cases.
• a ratio of the molar number of the mercapto compound of the general formula I and the molar number of the whole monomer to give the molecular weight in the above range is preferably in the range of 0.005:1 to 0.1:1, more preferably in the range of 0.01:1 to 0.1:1, further preferably in the range of 0.02:1 to 0.1:1.
• a molar number of the mercapto compound of the general formula I is 10 mol % or more based on the molar number of the whole monomer to be used, preferably 10 mol % to 60 mol %, and further preferably 10 mol % to 40 mol %.
• a polymer having a polysiloxane skeleton is formed in the polymerization system.
• the polysiloxane skeleton formed at this time may have different structures of the skeleton in the case where the mercapto compound of the general formula I has 2 alkoxy groups and in the case where it has 3 alkoxy groups.
• R 1 is an alkyl group in the general formula I
• a polymer having a linear polysiloxane skeleton as mentioned below is formed.
• R 1 and Y 1 have the same meanings as defined above.
• the obtained polymer of the present invention in this case is a polymer in which a unit having the above-mentioned polyorganosiloxane structure and a unit having a polymerizable double bond group, and a carboxyl group or a sulfonate group at the side chain are bonded by a sulfur atom.
• a monomer to provide a polymerizable double bond group or a monomer to provide a carboxyl group or a sulfonate group, at the side chain may be mentioned the same monomer as the various monomers to be used for obtained a polymer having a group represented by the general formula II at the end of the main chain, and having a polymerizable double bond group, and a carboxyl group or a sulfonate group at the side chain shown above.
• the substituents R 8 , R 9 , R 10 and R 11 each represents an alkyl group having 1 to 10 carbon atoms such as a methyl group, ethyl group, etc., preferably 1 to 6 carbon atoms, further preferably 1 to 4 carbon atoms, an alkoxy group having 1 to 10 carbon atoms such as a methoxy group, ethoxy group, etc., preferably 1 to 6 carbon atoms, further preferably 1 to 4 carbon atoms, or an aryl group which may have a substituent(s) having 6 to 12 carbon atoms such as a phenyl group, etc., preferably 6 to 10 carbon atoms, provided that at least two of R 8 , R 9 , R 10 and R 11 are alkoxy groups.
• Preferred examples of the compound represented by the general formula V may be mentioned compounds such as tetramethylorthosilicate, tetraethylorthosilicate, tetrapropylorthosilicate, tetrabutylorthosilicate, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, trimethoxypropylsilane, isobutyltrimethoxysilane, octyltrimethoxysilane, octadecyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, etc., and a plural kinds of compounds may be selected from these compounds.
• mercapto compound represented by the general formula I alone or in combination with the silane compound represented by the general formula V, and they are subjected to hydrolysis in the presence of water, and following polycondensation to form a polyorganosiloxane structural unit having a mercapto group at the side chain.
• a ratio of the whole molar number in which the molar numbers of the mercapto compound of the general formula I and the silane compound of the general formula V are combined based on the molar number of the whole monomer to be used in the graft polymerization is preferably 10 mol % or more, and similarly in the case where a polyorganosiloxane is synthesized by the mercapto compound of the general formula I alone and it is used for the graft polymerization, preferably 10 mol % to 60 mol %, further preferably 10 mol % to 40 mol %.
• the polyorganosiloxane structural unit can be formed with good yield.
• an inorganic acid such as hydrochloric acid, nitric acid, sulfuric acid, etc.
• an organic acid such as p-toluenesulfonic acid, p-toluenesulfonic acid monohydrate, sulfonic acid, methanesulfonic acid, ethanesulfonic acid, acetic acid, formic acid, etc.
• a metal hydroxide such as sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, etc.
• a carbonate such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, etc.
• a metal alkoxide such as sodium methoxide, sodium ethoxide, potassium methoxide, potassium t-butoxide, magnesium methoxide, magnesium ethoxide, etc.
• a primary amine such as methylamine, ethylamine, butylamine, monoethanolamine, etc.
• a secondary amine such as diethylamine, dibutylamine, etc.
• a tertiary amine such as triethylamine, diisopropylethylamine, dimethylaminoethanol, triethanolamine, etc.
• a nitrogen-containing heterocyclic ring compound such as pyridine, 1,8-
• An amount of the acid catalyst or base catalyst to be used is generally in the range of 0.001 parts by weight to 25 parts by weight, preferably 0.01 parts by weight to 20 parts by weight based on the total silane compound to be used as 100 parts by weight.
• the reaction temperature is generally a temperature range of from 0° C. to a boiling point of the solvent to be used, preferably in the range of 15° C. to 130° C. If the reaction temperature is too low, there is a case where progress of the condensation reaction becomes insufficient. On the other hand, if the reaction temperature is too high, it becomes difficult to prevent from gellation. The reaction is generally completed within several minutes to several 10 hours.
• the molecular weight of the polyorganosiloxane structural unit is preferably in the range of from 500 to 20,000, more preferably in the range of 1,000 to 10,000, further preferably in the range of 1,000 to 8,000 in a weight average molecular weight in terms of polystyrene. If it is less than the above molecular weight, there is a case where the effects of the present invention are not obtained in some cases. Also, if the molecular weight exceeds 20,000, there is a case where a solvent-insoluble gel is formed in some cases whereby a uniform polymer of the present invention cannot be obtained in some cases.
• the method for introducing the polymerizable double bond group is the same as the case of the polymer of the present invention having a group of the general formula II at the end of the main chain mentioned above.
• the specific synthetic method it is explained in more detail by the following mentioned Synthetic examples.
• the light-sensitive lithographic printing plate material of the present invention is characterized in that the photo-curable light-sensitive layer on the support is synthesized by using the compound represented by the above-mentioned formula I, and contains the polymer having a polymerizable double bond group, and a carboxyl group or a sulfonate group at the side chain, and as the other components, there may be mentioned the following components.
• a photopolymerization initiator generating a radical by photo-irradiation is preferably contained.
• optional compounds can be used so long as it basically forms a radical other than the following exemplified various compounds.
• photopolymerization initiator there may be mentioned, for example, (a) aromatic ketones, (b) organic peroxides, (c) hexaarylbiimidazole compounds, (d) ketoxime ester compounds, (e) azinium compounds, (f) titanocene compounds, (g) trihaloalkyl-substituted compounds and (h) organic boron salt compounds, etc.
• Preferred examples of the (a) aromatic ketones as the photopolymerization initiator may be mentioned, a compound having a benzophenone skeleton or thioxanthone skeleton, ⁇ -thiobenzophenone compounds disclosed in JP S47-6416B, benzoin ether compounds disclosed in JP 547-3981B, ⁇ -substituted benzoin compounds disclosed in JP 547-22326B, benzoin derivatives disclosed in JP 547-23664B, aroylphosphonic acid esters disclosed in JP 557-30704B, dialkoxybenzophenones disclosed in JP 560-26483B, benzoin ethers disclosed in JP S60-26403B and JP S62-81345A, p-di(dimethylaminobenzoyl)benzene disclosed in JP H2-211452A, a thio-substituted aromatic ketone disclosed in JP S61-194062A, acylphosphine
• organic peroxide which is other examples of the photopolymerization initiator according to the present invention
• organic compounds having one or more oxygen-oxygen bondings in the molecule are included, and there may be preferably mentioned, for example, peroxide esters such as 3,3′,4,4′-tetra(t-butylperoxycarbonyl)benzophenone, 3,3′,4,4′-tetra(t-amylperoxycarbonyl)benzophenone, 3,3′,4,4′-tetra(t-hexylperoxycarbonyl)benzophenone, 3,3′,4,4′-tetra(t-octylperoxycarbonyl)benzophenone, 3,3′,4,4′-tetra(cumylperoxycarbonyl)benzophenone, 3,3′,4,4′-tetra(p-isopropylcumylperoxycarbonyl)benzophenone, di-t-butyl-diperoxyis
• lophine dimers disclosed in JP S45-37377B and JP S44-86516B, for example, 2,2′-bis(o-chlorophenyl)-4,4′,5,5′-tetraphenylbiimidazole, 2,2′-bis(o-bromophenyl)-4,4′,5,5′-tetraphenylbiimidazole, 2,2′-bis(o,p-dichlorophenyl)-4,4′,5,5′-tetraphenylbiimidazole, 2,2′-bis(o-chlorophenyl)-4,4′,5,5′-tetra(m-methoxyphenyl)biimidazole, 2,2′-bis(o,o′-dichlorophenyl)-4,4′,5,5′
• (d) ketoxime ester which is other examples of the photopolymerization initiator according to the present invention
• 3-benzoyloxy-iminobutan-2-one 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-p-toluenesulfonyloxyiminobutan-2-one, 2-ethoxy-carbonyloxyimino-1-phenylpropan-1-one, etc.
• Examples of the (e) azinium salt compound which is other examples of the photopolymerization initiator may be mentioned compound groups having a N—O bond as disclosed in JP S63-138345A, JP S63-142345A, JP S63-142346A, JP S63-143537A and JP S46-42363B.
• Examples of the (f) titanocene compound which is other examples of the photopolymerization initiator may be mentioned, for example, various titanocene compounds as disclosed in JP S59-152396A, JP S61-151197A, JP S63-41483A, JP S63-41484A, JP H2-249A, JP H2-291A, JP H3-27393A, JP H3-12403A, JP H6-41170A, etc., and they can be preferably used.
• titanocene compounds may be mentioned, for example, di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4,6-trifluorophen-1-yl, di-cyclopentadienyl-Ti-2,6-di-fluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4-di-fluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, di-methylcyclopentadie
• trihaloalkyl-substituted compound As the other examples of the photopolymerization initiator, there may be mentioned (g) trihaloalkyl-substituted compound.
• the trihaloalkyl-substituted compound herein mentioned specifically means a compound having at least one trihaloalkyl group such as a trichloromethyl group, tribromomethyl group, etc., in the molecule.
• Preferred examples may be mentioned s-triazine derivatives and oxadiazole derivatives as a compound in which said trihaloalkyl group is bonded to a nitrogen-containing heterocyclic ring group, or trihaloalkylsulfonyl compounds in which said trihaloalkyl group is bonded to an aromatic ring or nitrogen-containing heterocyclic ring through a sulfonyl group.
• trihaloalkyl-substituted compounds are mentioned below.
• an organic boron salt compound can be mentioned, and a compound having an organic boron anion represented by the following mentioned general formula VI is particularly preferably used.
• R 12 , R 13 , R 14 and R 15 each may be the same or different from each other, and each represent an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a heterocyclic ring group. Of these, particularly preferred is the case where one of the R 12 , R 13 , R 14 and R 15 is an alkyl group, and the other substituents are aryl groups.
• a cation which forms a salt therewith is simultaneously present.
• an alkali metal ion, onium ion and cationic sensitizing dye As the onium salt, there may be mentioned an ammonium, sulfonium, iodonium and phosphonium compound.
• a sensitizing dye is separately added to provide light-sensitivity in the wavelength of the light absorbed by the dye.
• an organic boron anion is contained as a counter anion of the cationic sensitizing dye, light-sensitivity is provided depending on an absorption wavelength of said sensitizing dye.
• an organic boron anion is preferably further contained in combination as a counter anion of the alkali metal or onium salt.
• organic boron salt to be used in the present invention there may be mentioned a salt containing the organic boron anion represented by the aforementioned general formula VI, and as a cation which forms a salt, there may be preferably used an alkali metal ion and an onium compound.
• an onium salt with the organic boron anion ammonium salts such as tetraalkyl ammonium salt, etc., sulfonium salts such as triarylsulfonium salt, etc., and phosphonium salts such as triarylalkylphosphonium salt, etc.
• ammonium salts such as tetraalkyl ammonium salt, etc.
• sulfonium salts such as triarylsulfonium salt, etc.
• phosphonium salts such as triarylalkylphosphonium salt, etc.
• Particularly preferred examples of the organic boron salt are mentioned below.
• photopolymerization initiator which can be most preferably used in the present invention, there may be mentioned the above-mentioned trihaloalkyl-substituted compound and organic boron salt compound, or the case where these are used in combination.
• the photopolymerization initiator is preferably used in the range of 0.1 to 30 parts by weight based on 100 parts by weight of said polymer, and further, particularly preferably in the range of 0.2 to 20 parts by weight.
• an organic boron salt compound As the most preferred photopolymerization initiator to provide a light-sensitive lithographic printing plate material which is excellent in plate preservation stability and background stain property, or excellent in adhesiveness or abrasion resistance which are objects of the present invention, there may be mentioned an organic boron salt compound, and also a system in which the above-mentioned trihaloalkyl-substituted compound and the organic boron salt are contained in combination.
• photocurability can be synergistically promoted, and extremely good adhesiveness and abrasion resistance can be realized in combination with the polymer of the present invention.
• the photo-curable light-sensitive layer of the light-sensitive lithographic printing plate material it is preferred to contain a compound having a peak of sensitivity with a light wavelength region of 400 to 430 nm or 750 to 1100 nm, having an absorption in this wavelength region, and sensitizing the above-mentioned photopolymerization initiator in combination.
• the compounds which increase the sensitivity at the wavelength region of 400 to 430 nm may be mentioned cyanine series dyes, coumarine series compounds as disclosed in JP H7-271284A, JP H8-29973A, etc., carbazole series compounds as disclosed in JP H9-230913A, JP 2001-42524A, etc., carbomelocyanine series dyes as disclosed in JP H8-262715A, JP H8-272096A, JP H9-328505A, etc., aminobenzylidene ketone series dyes as disclosed in JP 114-194857A, JP 116-295061A, JP H7-84863A, JP H8-220755A, JP H9-80750A, JP H9-236913A, etc., pyromethine series dyes as disclosed in JP H4-184344A, JP H6-301208A, JP H7-225474A, JP H7-5685A, JP H7
• Examples of coumarine series compound which can be used to increase the sensitivity in the wavelength region of 400 to 430 nm are mentioned below.
• cyanine series dyes As a sensitizing dye in the wavelength region of 750 to 1100 nm, there may be mentioned cyanine series dyes, porphyrin, spiro compounds, ferrocene, fluorene, fulgide, imidazole, perylene, phenazine, phenothiazine, polyene, azo series compounds, diphenylmethane, triphenylmethane, polymethineacridine, coumarin, ketocoumarine, quinacridone, indigo, styryl, squarylium series compounds, and (thio)pyrylium series compounds, and further, the compounds disclosed in EP Patent No. 568,993, U.S. Pat. No. 4,508,811 and U.S. Pat. No. 5,227,227 can be used.
• sensitizing dyes which correspond to near infrared light in the wavelength region of 750 to 1100 nm are mentioned below.
• a polyfunctional monomer may be contained.
• a polyfunctional monomer such as 1,4-butanediol di(meth)acrylate, 1,6-hexane-diol di(meth)acrylate, neopentylglycol di(meth)acrylate, tetraethylene glycol di(meth)-acrylate, trisacryloyloxyethylisocyanurate, tripropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, etc., or as various polymers into which a (meth)acryloyl group has been introduced, there may be mentioned polyester(meth)acrylate, urethane
• the photo-curable light-sensitive layer As other element(s) for constituting the photo-curable light-sensitive layer, it is preferably carried out to add various dyes and pigments for the purpose of heightening visibility of an image, or to add inorganic fine particles or organic fine particles for the purpose of preventing blocking of the light-sensitive composition and others.
• a polymerization inhibitor is preferably added to prevent from curing reaction by thermal polymerization in a dark place during the long term preservation.
• the polymerization inhibitor to be used for the above purpose there may be preferably used various kinds of compounds having phenolic hydroxyl group(s) such as hydroquinones, catechols, naphthols, cresols, etc., quinone compounds, 2,2,6,6-tetramethylpiperidine-N-oxyls, N-nitrosophenylhydroxylamine salts, etc.
• An added amount of the polymerization inhibitor to be used in this case is preferably in the range of 0.01 parts by weight to 10 parts by weight based on the total solid content of the photo-curable light-sensitive layer as 100 parts by weight.
• plastic film supports there may be mentioned various plastic film supports and aluminum plates.
• plastic film supports there may be representatively mentioned polyethylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, polystyrene, polyvinyl acetal, polycarbonate, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose nitrate, etc., and polyethylene terephthalate or polyethylene naphthalate is particularly preferably used.
• the surfaces of these films are preferably subjected to hydrophilic treatment on the film surface thereof before providing a layer using the light-sensitive lithographic printing plate material of the present invention.
• Such a hydrophilic processing may be mentioned a corona discharge treatment, flame treatment, plasma treatment, UV irradiation treatment, etc.
• a further hydrophilic treatment it may be preferably carried out by providing a layer containing various water-soluble polymers on the film.
• it is preferably carried out to form a hydrophilic layer comprising a water-soluble polymer, colloidal silica and a cross-linking agent as described in the above-mentioned JP 2008-250195A (Patent Literature 1) on the above-mentioned film.
• a subbing layer may be provisionally provided on the film to heighten adhesiveness with the hydrophilic layer to be provided therein.
• a layer mainly comprising a hydrophilic resin is effective.
• hydrophilic resin preferably used are hydrophilic resins such as gelatin, gelatin derivative (for example, phthalated gelatin), hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, hydroxypropylmethyl cellulose, ethylhydroxyethyl cellulose, polyvinylpyrrolidone, polyethylene oxide, xanthane, cationic hydroxyethyl cellulose, polyvinyl alcohol, polyacrylamide, etc.
• gelatin and polyvinyl alcohol are particularly preferred.
• an aluminum plate having an anodized film which had been subjected to roughening treatment is preferably used.
• an aluminum plate a surface of which is subjected to silicate treatment is also preferably used.
• an aluminum plate on the surface of which is formed the above-mentioned hydrophilic layer may be used.
• a layer containing the polymer of the present invention, a photopolymerization initiator, a sensitizer and other materials mentioned above is formed on the support surface as a photo-curable light-sensitive layer or on the support surface via the above-mentioned hydrophilic layer.
• a coating amount of a dry solid content of the photocurable light-sensitive layer itself in this case, it is preferably formed with a coating amount of the dry solid content in the range of 0.3 g to 10 g per 1 m 2 with a dry weight, and further when it is in the range of 0.5 g to 3 g, it develop good resolution, and ensures printing endurance of fine line image or fine dot image, and simultaneously abrasion resistance can be markedly improved so that it is particularly preferred.
• the photo-curable light-sensitive layer was formed by preparing a solution in which the above-mentioned various elements are mixed, and coating on the support surface or on the hydrophilic layer by using conventionally known various coating systems and dried.
• the light-sensitive lithographic printing plate material of the present invention it is also preferably carried out to further form a protective layer on the photo-curable light-sensitive layer comprising the photopolymerizable composition.
• the protective layer has preferred effects that it prevents from migration of a low molecular weight compound such as oxygen or basic substance, etc. existing in the air, which inhibits an image forming reaction caused by exposure in the light-sensitive layer into the light-sensitive layer, and further improves exposure sensitivity in the air. Moreover, it is also expected to have an effect that the surface of the light-sensitive layer is prevented from flaw.
• the characteristics desired for such a protective layer are low transmittance of a low molecular weight compound such as oxygen, etc., excellent in dynamic strength, further, substantially not inhibit transmission of light to be used for exposure, excellent in adhesiveness with the light-sensitive layer, and, easily removable during the developing step after exposure.
• a low molecular weight compound such as oxygen, etc.
• said polymer contained in the photo-curable light-sensitive layer as mentioned above is water-soluble so that there are some cases causing problems that it absorbs moisture in the air to cause blocking, or causing change in sensitivity during preservation.
• a protective layer at the upper portion of the photo-curable light-sensitive layer, it is possible to cancel these problems such as blocking and change in sensitivity.
• laser output is generally lower as compared with that of a near infrared semiconductor laser, so that a light-sensitive layer having particularly high sensitivity is required.
• sensitivity is further increased so that it can be particularly preferably applied.
• Such a device concerning the protective layer has heretofore been carried out, and described in detail in U.S. Pat. No. 3,458,311, JP S55-49729A, etc.
• a material which can be used for the protective layer there may be preferably used, for example, a water-soluble polymer compound which is relatively excellent in crystallinity. More specifically, a water-soluble polymer such as a polyvinyl alcohol, polyvinylpyrrolidone, acidic celluloses, gelatin, gum Arabic, polyacrylic acid, etc., has been known, and of these, when polyvinyl alcohol is used as a main component, most excellent results can be obtained on the basic characteristics such as an oxygen shielding property, removability in development.
• the polyvinyl alcohol to be used in the protective layer may be substituted by an ester, ether, and acetal in a part thereof so long as it contains an unsubstituted vinyl alcohol unit for having necessary oxygen-shielding property and water-solubility. Also, a part thereof may have other copolymerizable component similarly.
• a coating amount with a dry solid content when such a protective layer is to be applied there exist a preferred range, and the coating amount with the dry solid content is preferably formed on the light-sensitive layer in terms of a dry weight in the range of 0.1 g to 10 g per 1 m 2 in a dry weight, more preferably in the range of 0.2 g to 2 g.
• the protective layer is coated on the photo-curable light-sensitive layer by using the conventionally known various coating systems and dried.
• a material having a photo-curable light-sensitive layer formed on a support as mentioned above as a printing plate it is subjected to contact exposure or laser scanning exposure, whereby the exposed portions are cross-linked so that their solubilities are lowered, and the unexposed portion is dissolved out by using a neutral developing solution having a pH of less than 9 or an alkali developing solution having a pH in the range of 9 to 12 to carry out pattern formation.
• a neutral developing solution having a pH of less than 9 means a pH in the range of 4 to less than 9, preferably a pH in the range of 6 to less than 9, and most preferably it contains substantially no chemical agent.
• various inorganic or organic ionic compounds may be contained in pure water with a concentration of 1% by weight or less, and it may be water containing a sodium, potassium, calcium, magnesium ion, etc. Or else, various surfactants, etc., may be contained in water with a concentration of 1% by weight or less.
• various alcohols such as methanol, ethanol, propanol, isopropanol, ethylene glycol, propylene glycol, methoxyethanol, polyethylene glycol, etc.
• water may be contained in water as a solvent with a concentration of 1% by weight or less.
• various gum liquids are added in a concentration of 1% by weight or less and development may be preferably carried out for the purpose of protecting the plate surface from fingerprint stain, etc.
• the light-sensitive lithographic printing plate material of the present invention can show good characteristics as a printing plate even when an alkali developing solution having a pH in the range of 9 to 12 other than the above-mentioned neutral developing solution.
• a developing solution may contain a surfactant and an alkaline agent.
• an organic solvent, buffer, chelating agent, etc. may be further contained.
• Suitable alkaline agent may be mentioned an inorganic alkaline agent such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium triphosphate, sodium diphosphate, sodium carbonate, potassium carbonate, sodium bicarbonate, etc., or an organic amine compound such as trimethylamine, diethylamine, isopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamines, etc., and these compounds may be used singly or in combination.
• an inorganic alkaline agent such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium triphosphate, sodium diphosphate, sodium carbonate, potassium carbonate, sodium bicarbonate, etc.
• an organic amine compound such as trimethylamine, diethylamine, isopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamines, etc., and these compounds may be used singly or in combination.
• nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, etc.
• anionic surfactants such as alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkylsulfates, alkylsulfonates, sulfosuccinate esters, etc.
• amphoteric surfactants such as alkylbetaines, amino acids, etc.
• organic solvents it is possible to contain, for example, isopropyl alcohol, benzylalcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol, etc., if necessary.
• a developing solution containing tetraalkyl ammonium hydroxide with a pH 10 to 12 as described in JP 2006-39177A or JP 2006-64952A, etc. can be preferably used.
• the alkyl group of the tetraalkyl ammonium hydroxide in this case, an alkyl group having 1 to 6 carbon atoms is preferred, and an alkyl group having 1 to 4 carbon atoms is particularly preferred.
• These alkyl groups may be further substituted by a hydroxyl group, an alkoxy group such as a methoxy group, etc.
• the developing method is not particularly limited, and there may be mentioned a method in which the material is dipped in a developing solution, a method in which a non-image portion which is being dissolved by a developing solution is removed physically by a brush, etc., a method in which a developing solution is sprayed to the material to remove a non-image portion, and the like.
• a developing time may be selected depending on the above-mentioned developing method so that an unexposed portion can be sufficiently removed, and optionally selected from the range of 5 seconds to 10 minutes.
• a hydrophilic treatment, etc., using gum Arabic, etc. may be optionally carried out.
• an oxygen-shielding layer may be previously washed before development.
• a gum coating treatment for the purpose of protecting the plate surface may be carried out to prevent the surface of the printing plate from flaw or stain by using a gum liquid such as gum Arabic, etc.
• M-1 a compound represented by the chemical formula M-1 was obtained from p-chloromethylstyrene (CMS-14 available from AGC SEIMI CHEMICAL CO., LTD.) and bismuthiol. 60 parts of M-1 and 40 parts of methacrylic acid were added to 170 parts of ethanol and 30 parts of distilled water, and 62 parts of dimethylaminoethanol was added to the mixture to uniformly dissolve the same.
• the mixture was transferred onto the water bath heated at 75° C., 5 parts of 3-mercaptopropyl(dimethoxy)methylsilane was added to the mixture, and 1 part of azobisisobutyronitrile (AIBN) was immediately added to the mixture as a polymerization initiator to start the polymerization.
• AIBN azobisisobutyronitrile
• a mol % of the mercapto compound based on the whole monomer in this case was 4.0%.
• the mixture was stirred at an inner temperature of 73° C. for 10 hours, and then, cooled to room temperature.
• Distilled water was added to make up the whole amount 1 liter, and 1 part of Cupferron (N-nitrosophenylhydroxylamine ammonium salt) was added to the mixture as a polymerization inhibitor, and 35 parts of p-chloromethylstyrene (CMS-14 available from AGC SEIMI CHEMICAL CO., LTD.) was further added to the mixture, and the resulting mixture was stirred at 40° C. for 5 hours.
• Hydrochloric acid was gradually added to the mixture under ice-cooling to lower the pH of the same to 2, and the precipitated sediments were separated by filtration. The sediments were washed with distilled water and dried in a vacuum dryer to obtain a polymer having a structure shown by AP-4.
• a precursor polymer graft-polymerized to the polyorganosiloxane was obtained.
• a molecular weight of the obtained precursor polymer was measured by an aqueous GPC.
• a weight average molecular weight of said precursor polymer graft-polymerized was about 50,000.
• the total amount of the silane compound used for synthesis of the polyorganosiloxane was 0.236 mol %, and a ratio thereof based on the whole monomer used for the graft polymerization was 44 mol %.
• Synthesis of a comparative polymer having no polyorganosiloxane structural unit is carried out. That is, 30 parts of p-chloromethylstyrene (CMS-14 available from AGC SEIMI CHEMICAL CO., LTD.), 70 parts of acrylamide-2-methylpropanesulfonic acid (ATBS available from TOAGOSEI CO., LTD.) and 52 parts of dimethylaminoethanol were charged and dissolved. Heating was carried out at 70° C., and under nitrogen atmosphere, 1 part of azobisisobutyronitrile (AIBN) was added to the mixture as a polymerization initiator to carry out polymerization. The mixture was stirred at 70° C. for 6 hours to obtain a polymer.
• CMS-14 p-chloromethylstyrene
• ATBS acrylamide-2-methylpropanesulfonic acid
• AIBN azobisisobutyronitrile
• the obtained precursor polymer was carried out measurement of the molecular weight by aqueous GPC.
• the weight average molecular weight of the graft-polymerized precursor polymer was about 100,000.
• total amount of the silane compound used for synthesis of the polyorganosiloxane was 0.29 mol %, and a ratio thereof to the whole monomer used for the graft polymerization was 33 mol %.
• CMS-14 p-chloromethylstyrene
• Hydrochloric acid was gradually added under ice-cooling to lower the pH of the reaction system to 2, and the precipitated sediments were separated by filtration.
• the sediments were washed with distilled water and dried in a vacuum dryer to obtain a polymer of the present invention having a structure shown in the following estimated chemical formula.
• the numerals represent parts by weight.
• Comparative polymer having no polyorganosiloxane structural unit was carried out. 80 parts of M-1 was charged, then, 120 parts of acrylamide-2-methylpropanesulfonic acid and 80 parts of dimethylaminoethanol were added thereto, and the whole mixture was heated to 70° C. under a nitrogen atmosphere to dissolve the same. As a polymerization initiator, 2 parts of AIBN was added to the solution to initiate polymerization, and the mixture was stirred at 70° C. for 10 hours.
• Synthesis of a comparative polymer having no polyorganosiloxane structural unit was carried out.
• a mixed solvent of 150 parts of ethanol and 30 parts of distilled water was added 60 parts of M-1, then, further 40 parts of methacrylic acid and 62 parts of dimethylaminoethanol were added to the mixture, and under a nitrogen atmosphere, the whole mixture was heated at 70° C. to dissolve the components.
• To the mixture was added 1 part of AIBN as a polymerization initiator to initiate polymerization, and the mixture was stirred at 70° C. for 10 hours.
• the light-sensitive lithographic printing plate materials prepared as mentioned above was subjected to exposure test as follows. Exposure was carried out by using PT-R4000 (manufactured by DAINIPPON SCREEN MFG. CO., LTD.) mounting a laser having a light wavelength of 830 nm, setting an exposure energy to 100 mJ/cm 2 using the device, with a drum rotation number of 1,000 rpm. As an image for the test, halftone gradation pattern showing dot area from 1% to 97% corresponding to 2400 dpi and 175 lines; fine lines of 10 to 100 ⁇ m; and solid image were output to carry out evaluation of the following mentioned resolution.
• PT-R4000 manufactured by DAINIPPON SCREEN MFG. CO., LTD.
• Each light-sensitive lithographic printing plate subjected to drawing as mentioned above was immersed in water controlled to 30° C. for 10 seconds, and the surface was rubbed by a sponge softly to remove the unexposed portion.
• developability evaluation the case where the unexposed portion was completely removed was judged as ⁇ , the case where a remaining film was slightly admitted at the unexposed portion was judged as ⁇ , and the case where developability was poor and a remaining film or developing failure was clearly caused was judged as X.
• Example 1 Example 2
• Example 3 Example 4 Water ⁇ ⁇ ⁇ ⁇ developability Resolution ⁇ ⁇ ⁇ ⁇ Comparative Comparative Comparative example 1 example 2 example 3 example 4 Water ⁇ ⁇ X X developability Resolution ⁇ ⁇ ⁇ ⁇ ⁇
• the ink on the printing plate was wiped off with a cleaner solution each 10,000 sheets from starting the printing, and then, reflection density at the solid portion in the test image was measured by using a reflection densitometer DM-620 manufactured by DAINIPPON SCREEN MFG. CO., LTD., and it was evaluated by observing lowering in reflection density during the printing.
• Table 2 The results are summarized in Table 2.
• Example 1 Example 2
• Example 3 Example 4 Reflection density Start 1.6 1.6 1.6 1.6 10,000 sheets 1.2 1.4 1.5 1.6 20,000 sheets 1.0 1.3 1.5 1.6 30,000 sheets 0.9 1.1 1.4 1.5 40,000 sheets 0.8 1.0 1.4 1.4 50,000 sheets 0.7 0.9 1.4 1.4 Printing endurance Start ⁇ ⁇ ⁇ ⁇ 10,000 sheets ⁇ ⁇ ⁇ ⁇ 20,000 sheets ⁇ ⁇ ⁇ ⁇ 30,000 sheets ⁇ ⁇ ⁇ ⁇ 40,000 sheets ⁇ ⁇ ⁇ ⁇ 50,000 sheets ⁇ ⁇ ⁇ ⁇ Comparative Comparative Comparative Comparative example 1 example 2 example 3 example 4 Reflection density Start 1.6 1.6 1.6 1.6 1.6 10,000 sheets 1.2 1.2 1.1 1.4 20,000 sheets 0.8 1.1 0.8 1.1 30,000 sheets 0.5 0.7 0.5 0.8 40,000 sheets 0.3 0.6 0.4 0.5 50,000 sheets 0.2 0.5 0.3 0.3 Printing endurance Start ⁇ ⁇ ⁇ 10,000 sheets ⁇ ⁇ ⁇ 20,000 sheets X ⁇ ⁇ ⁇
• Polyacrylamide-acrylic acid 80/20 copolymer 10% aqueous 100 parts solution Colloidal silica (Snowtex PS-S available from Nissan 100 parts Chemical Co., Ltd.) (20% concentration) Epoxy cross-linking agent (DENACOL EX-512 available 2 parts from NAGASE & CO., LTD.) raw solution Distilled water 100 parts
• a coating solution of the following mentioned photocurable light-sensitive layer prescription 2 was prepared, and coated on the above-mentioned hydrophilic layer and dried to for a photo-curable light-sensitive layer, to prepare each light-sensitive lithographic printing plate material of Examples 5 to 8.
• a coated amount of the photo-curable light-sensitive layer was so set to become 1.6 g per 1 m 2 in a dry weight by using a wire bar. Drying was carried out by using a dryer at 80° C. for 10 minutes.
• the photo-curable light-sensitive layer by using a polyvinyl alcohol (PVA-105 available from KURARAY CO., LTD.) as a protective layer, coating was carried out so that a dry coated weight became 2.0 g per 1 m 2 by using a wire bar. Drying was carried out by using a dryer at 80° C. for 10 minutes.
• PVA-105 available from KURARAY CO., LTD.
• the light-sensitive lithographic printing plate materials prepared as mentioned above was subjected to exposure test as follows. Exposure was carried out by using an image setter VIPLAS (manufactured by Mitsubishi Paper Mills Limited) for CTP mounted thereon a semiconductor laser with a light wavelength of 405 nm, setting an exposure energy on the plate surface to 80 mJ/cm 2 using the device, and image drawing was carried out by the scanning exposure system. As an image for the test, halftone gradation pattern showing dot area from 1% to 97% corresponding to 2400 dpi and 175 lines; fine lines of 10 to 100 min; and solid image were output to carry out evaluation of the following mentioned resolution.
• Each light-sensitive lithographic printing plate subjected to drawing as mentioned above was immersed in water controlled to 30° C. for 10 seconds, and the surface was rubbed by a sponge softly to remove the unexposed portion.
• developability evaluation the case where the unexposed portion was completely removed was judged as ⁇ , the case where a remaining light-sensitive layer was slightly admitted was judged as ⁇ , and the case where developability was poor and a remaining film or developing failure was clearly caused was judged as X.
• the ink on the printing plate was wiped off with a cleaner solution each 10,000 sheets from starting the printing, and then, reflection density at the solid portion in the test image was measured by using a reflection densitometer DM-620 manufactured by DAINIPPON SCREEN MFG. CO., LTD., and it was evaluated by observing lowering in reflection density during printing.
• Table 4 The results are summarized in Table 4.
• An aluminum plate in which an anodized aluminum plate having a thickness of 0.24 mm which had been carried out a sand-grained treatment was further subjected to silicate treatment using sodium silicate was used as a support.
• the polymers shown in Table 5 were used as a polymer, coating solutions with the following mentioned photo-curable light-sensitive layer prescription 3 were prepared, and each solution was coated on said aluminum plate and dried to prepare light-sensitive lithographic printing plate materials of Examples 9 to 11.
• AP-2 used in Example 9 was synthesized by polymerizing 65 parts of allyl methacrylate and 35 parts of acrylic acid in the presence of 7 parts of trimethoxy silane according to the conventionally known method.
• a coating solution with the photo-curable light-sensitive layer prescription 3 was simultaneously prepared in the same manner as mentioned above by using the polymer obtained in Comparative synthetic example 3, and the solution was coated on said aluminum plate and dried to prepare a comparative light-sensitive lithographic printing plate material of Comparative example 7.
• a coated amount of the photo-curable light-sensitive layer was so set and coated to be 1.8 g per 1 m 2 with a dry weight by using a wire bar. Drying was carried out by using a dryer at 80° C. for 10 minutes.
• photo-curable light-sensitive layers as a protective layer, by using a polyvinyl alcohol (PVA-105 available from KURARAY CO., LTD.), it was coated so that a dry coated weight became 2.0 g per 1 m 2 by using a wire bar. Drying was carried out by using a dryer at 80° C. for 10 minutes.
• PVA-105 available from KURARAY CO., LTD.
• the light-sensitive lithographic printing plate materials prepared as mentioned above was subjected to exposure test as follows. Exposure was carried out by using an image setter VIPLAS (manufactured by Mitsubishi Paper Mills Limited) for CTP mounted thereon a semiconductor laser with a light wavelength of 405 nm, setting an exposure energy on the plate surface to 120 ⁇ J/cm 2 using the device, and image drawing was carried out by the scanning exposure system. As an image for the test, halftone gradation pattern from 1% to 97% corresponding to 2400 dpi and 175 lines; fine lines of 10 to 100 ⁇ m were output.
• the exposed light-sensitive lithographic printing plate materials were subjected to development by using the developing solution prepared by the following mentioned constitution. Development was carried out by using an automatic developing device P-1310T manufactured by Mitsubishi Paper Mills Limited and treatment was carried out at 30° C. for 15 seconds.
• the following mentioned hydrophilic layer coating solution prescription was coated thereon as a hydrophilic layer described in JP 2008-250195A using a wire bar so that a dry weight became 3 g per 1 m 2 . Drying was carried out in a dryer at 80° C. for 20 minutes. Each sample was further heated in a dryer at 40° C. for 3 days, and then, applied to the subsequent coating of a photo-curable light-sensitive layer.
• Polyacrylamide-acrylic acid 80/20 copolymer 10% aqueous 100 parts solution Colloidal silica (SNOWTEX PS-S, available from Nissan 100 parts Chemical Co., Ltd.) (20% concentration) Epoxy cross-linking agent (DENACOL EX-512, available 2 parts from NAGASE & CO., LTD.) raw solution Distilled water 100 parts
• the following mentioned photo-curable light-sensitive layer prescription 4 was prepared by using the polymer shown in Table 9, and coated on the above-mentioned hydrophilic layer and dried to obtain each light-sensitive lithographic printing plate material of Examples 16 to 19.
• a coating solution for the photo-curable light-sensitive layer prescription was prepared in the same manner by using the polymer obtained in Comparative synthetic example 2 as a polymer, and coated on said hydrophilic layer, and dried to obtain Comparative light-sensitive lithographic printing plate material of Comparative example 9.
• a coated amount of the photo-curable light-sensitive layer was so provided by using a wire bar that it became 2.0 g per 1 m 2 as a dry weight. Drying was carried out in a dryer at 80° C. for 10 minutes. Different from the above-mentioned Examples and Comparative examples, no protective layer was provided on the upper portions of these photo-curable light-sensitive layers.
• the obtained light-sensitive lithographic printing plate material was adhered to an aluminum plate with a thickness of 0.24 mm, and by using an image setter PT-R4000 (an image drawing device mounting a laser with 830 nm) for a thermal plate manufactured by DAINIPPON SCREEN MFG. CO., LTD., exposure was carried out by setting an exposure dose irradiated to the lithographic plate to 100 mJ/cm 2 .
• the exposed light-sensitive lithographic printing plate material was treated by using a developing solution which comprises distilled water alone, and using an automatic developing device P-1310T manufactured by Mitsubishi Paper Mills Limited as a developing device at 30° C. for 15 seconds.
• evaluation of printability was carried out, and printing endurance, background stain and background stain after plate preservation were evaluated. The results are summarized in Table 10.
• the light-sensitive lithographic printing plate material provided by the present invention has high sensitivity to laser which emits in the near infrared region (750 to 1100 nm) or in the wavelength region of 400 to 430 nm, and developable with water or an aqueous alkali solution having a pH of 12 or less, so that it is suitable not only for a printing plate for CTP utilizing the same but also for formation of a resist for preparing a printed wiring board, or a color filter, a fluorescent pattern, etc.

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